CN102653657B - Cationic electrodeposition coating composition - Google Patents
Cationic electrodeposition coating composition Download PDFInfo
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- CN102653657B CN102653657B CN201210048476.3A CN201210048476A CN102653657B CN 102653657 B CN102653657 B CN 102653657B CN 201210048476 A CN201210048476 A CN 201210048476A CN 102653657 B CN102653657 B CN 102653657B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a cationic electrodeposition coating composition that has excellent throwing power and that can form a thin film with excellent finish and anti-corrosion properties. The composition has a cationic epoxy resin (A) and a blocked polyisocyanate (B), the cationic epoxy resin (A) obtained by reacting an epoxy resin (A1) with an amino group-containing compound (A2). The epoxy resin (A1) having a catechol skeleton structure (a) and obtained by reacting an epoxy resin (a1) containing at least one epoxy group per molecule and having an epoxy equivalent of 180 to 500 with a phenolic hydroxyl group-containing compound (a2) containing at least one phenolic hydroxyl group per molecule in amounts wherein the ratio of the number of moles of epoxy groups in the epoxy resin (a1) to the number of moles of phenolic hydroxyl groups in the phenolic hydroxyl group-containing compound (a2) is 1.3 to 2.0.
Description
Technical field
Quoting of related application
The application requires the right of priority of the 2011-047061 Japanese patent application of submission on March 4th, 2011, and its whole content incorporated herein by reference.
The present invention relates to the cation electric deposition paint composition that there is excellent throwing power and can form the film (the desciccator diaphragm thickness especially with 10 μ m) with excellent finishability (hot-fluid performance) and Corrosion Protection.
Background technology
In using the electrocoating paint of cation electric deposition paint composition, attempt keeping the inner film thickness of bag part and gap portion to guarantee Corrosion Protection always, and make outer film thickness optimization or evenly (for example, guarantee wherein to pay attention to the film thickness of the part of finishability and Corrosion Protection) to improve body of a motor car quality and to reduce costs.
Yet, in using filming that conventional cation electric deposition paint composition obtains by galvanic deposit, reduce coating thickness and may cause the poor finishability that produces due to inhomogeneous base material and the reduction of hot-fluid performance.In addition, for the object of improving finishability, if the amount of plastic fraction that is increased in the middle use of filming to improve the hot-fluid performance in heating and drying process, polarization impedance reduces, " throwing power " of filming thus and Corrosion Protection tend to reduction.
Consider these situations, expectation exploitation has excellent throwing power and can form the cation electric deposition paint composition of the thin coating film (the desciccator diaphragm thickness especially with 10 μ m) with excellent finishability (hot-fluid performance) and Corrosion Protection.
Patent documentation 1 discloses and has comprised containing amino modified epoxy (A), the resin (B) of phenolic hydroxy group and the cation electric deposition paint composition of block polyisocyanate solidifying agent (C), it has excellent throwing power and can form and have filming of excellent finishability, and special to form the desciccator diaphragm thickness with excellent finishability and Corrosion Protection be filming of 15 μ m.Yet disclosed composition can not be entirely satisfactory aspect all throwing powers, finishability (hot-fluid performance) and the Corrosion Protection of thin coating film (the desciccator diaphragm thickness especially with 10 μ m).
Prior art document
1: the 2011-6655 Japanese Unexamined Patent Publication of patent documentation.Disclosure of an invention content
Technical problem
The object of this invention is to provide the cation electric deposition paint composition that there is excellent throwing power and can form the film (the desciccator diaphragm thickness especially with 10 μ m) with excellent finishability (hot-fluid performance) and Corrosion Protection.
The solution of problem
Present inventor carries out large quantity research to realize above-mentioned purpose.Result, present inventor finds that above-mentioned purpose can be realized by cation electric deposition paint composition, and it comprises: by making to react with the epoxy resin (A1) in a part for molecule with pyrocatechol skeleton structure (a) cation epoxy resin (A) obtaining containing amino compound (A2); And block polyisocyanate (B).Based on this discovery, complete the present invention.
More specifically, the present invention relates to following items:
1. cation electric deposition paint composition, it comprises cation epoxy resin A) and block polyisocyanate (B),
By making epoxy resin (A1) and reacting and obtain described cation epoxy resin (A) containing amino compound (A2), and
Described epoxy resin (A1) has the pyrocatechol skeleton structure (a) being represented by following general formula (1) in a part for described molecule
General formula (1)
Wherein R represents hydrogen atom or has the alkyl of 1 to 6 carbon atom, and react and obtain by the compound (a2) that makes per molecule comprise at least one epoxy group(ing) and to there is the phenolic hydroxy group that the epoxy resin (a1) of 180 to 500 epoxy equivalent (weight)s comprises at least one phenolic hydroxyl group with per molecule, the amount of described epoxy resin (a1) and the compound (a2) of described phenolic hydroxy group is that the ratio of the phenolic hydroxyl group mole number in the compound (a2) of epoxy group(ing) mole number in described epoxy resin (a1) and described phenolic hydroxy group is 1.3 to 2.0.
2. the cation electric deposition paint composition as described in project 1, wherein said epoxy resin (a1) comprise by make Epicholorohydrin be selected from pyrocatechol and alkyl pyrocatechol at least one react the epoxy resin obtaining.
3. the cation electric deposition paint composition as described in project 1, the compound of wherein said phenolic hydroxy group (a2) comprises at least one being selected from pyrocatechol and alkyl pyrocatechol.
4. the cation electric deposition paint composition as described in arbitrary project in project 1 to 3, the solids content based on described resin (A) wherein, the described pyrocatechol skeleton structure (a) that described cation epoxy resin (A) comprises 3% mass ratio to 65% mass ratio.
5. the cation electric deposition paint composition as described in arbitrary project in project 1 to 3, the solids content based on described resin (A) wherein, the described pyrocatechol skeleton structure (a) that described cation epoxy resin (A) comprises 5% mass ratio to 40% mass ratio.
6. the cation electric deposition paint composition as described in arbitrary project in project 1 to 5, the R in its formula of (1) represents to have the alkyl of 4 to 6 carbon atoms.
7. electrodeposition-coating method, it comprises step: base material is immersed in electrodeposition bath, wherein by the cation electric deposition paint composition described in arbitrary project in project 1 to 6 as described electrodeposition bath, and by described base material as negative electrode and apply electric current.
8. the coated article obtaining by base material described in method electrophoretic coating described in project 7.The beneficial effect of the invention
Cation electric deposition paint composition of the present invention has excellent " throwing power ", because the pyrocatechol skeleton structure (a) in introducing cation epoxy resin (A) has been accelerated the embryo deposit of electrodeposition coating, and the gratifying fusion bonding of filming is provided, can have applied high-voltage thus.In addition,, due to flexibility and the hot-fluid performance of filming and improving, therefore can obtain the coated article with " excellent film finishability " and " excellent film Corrosion Protection (the desciccator diaphragm thickness with 10 μ m) ".
Accompanying drawing summary
Fig. 1 is used the model diagram of " four layers of box throwing power test fixture " in throwing power test.
Fig. 2 is exemplified with the circuit for throwing power test electrodeposited coating.
The description of embodiment
The invention provides cation electric deposition paint composition, it comprises: cation epoxy resin (A) and block polyisocyanate (B), described epoxy resin (A) reacts and obtains with the epoxy resin (A1) in a part for molecule with pyrocatechol skeleton structure (a) by making to contain amino compound (A2).Be described in more detail below the present invention.
cation epoxy resin (A)
Cation epoxy resin in the present invention (A) reacts and obtains with the epoxy resin (A1) in a part for molecule with the pyrocatechol skeleton structure (a) being represented by following general formula (1) by making to contain amino compound (A2).
General formula (1)
(wherein R represents hydrogen atom or has the alkyl of 1 to 6 carbon atom).
While having the alkyl of 4 to 6 carbon atoms, there is excellent fusion bonding in the R in the pyrocatechol skeleton structure being represented by general formula (1), so it is preferred in the forming process of filming.
the epoxy resin (A1) in a part for molecule with pyrocatechol skeleton structure (a)
By the compound (a2) that makes per molecule comprise at least one epoxy group(ing) and to have a phenolic hydroxy group that the epoxy resin (a1) of 180 to 500 epoxy equivalent (weight)s comprises at least one phenolic hydroxyl group with per molecule, reacted and obtained epoxy resin (A1), the amount of described epoxy resin (a1) and the compound (a2) of described phenolic hydroxy group is that the ratio of the phenolic hydroxyl group mole number in the compound (a2) of epoxy group(ing) mole number in described epoxy resin (a1) and described phenolic hydroxy group is 2.0 to 1.3.
Pyrocatechol skeleton structure (a) is conventionally derived from epoxy resin (a1) and/or compound (a2), and is introduced in epoxy resin (A1).For example, resin (a1) can comprise by make Epicholorohydrin be selected from pyrocatechol and alkyl pyrocatechol at least one react the epoxy group(ing) obtaining, pyrocatechol skeleton structure (a) can be introduced in the resin matrix of epoxy resin (A1) thus.
The specific examples of epoxy resin (a1) comprises EPICLON HP-820 (by DIC Cos., Ltd. preparation).The example of alkyl pyrocatechol comprises 4-tert-butyl catechol, 4-methyl pyrocatechol, 2-methyl pyrocatechol etc.
Preferably by the epoxy resin by polyphenolic substance being reacted with Epicholorohydrin obtain as epoxy resin (a1) apart from the above.
The example that can be used to form the polyphenolic substance of this based epoxy resin comprises two (4-hydroxy phenyls)-2, 2-propane [dihydroxyphenyl propane], two (4-hydroxy phenyl) methane [Bisphenol F], two (4-hydroxy-cyclohexyl) methane [A Hydrogenated Bisphenol A F], 2, two (4-hydroxy-cyclohexyl) propane [Hydrogenated Bisphenol A] of 2-, 4, 4 '-dihydroxy benaophenonel, two (4-hydroxy phenyls)-1, 1-ethane, two (4-hydroxy phenyls)-1, 1-Trimethylmethane, two (4-hydroxyl-2 or 3-tert-butyl-phenyls)-2, 2-propane, two (2 hydroxy naphthalene base) methane, four (4-hydroxy phenyls)-1, 1, 2, 2-ethane, 4, 4 '-dihydroxy-diphenyl sulfone, linear phenolic aldehyde, cresol-novolak etc.
As the epoxy resin obtaining by polyphenolic substance is reacted with Epicholorohydrin, derived from dihydroxyphenyl propane the resin that represented by following general formula (2), be particularly preferred,
General formula (2)
Wherein q is 0 to 2.
The example of the commercially available product of epoxy resin comprises the Co. by Japan Epoxy Resins, those that Ltd sells with trade(brand)name " jER828EL " and " jER1001 ".
Can use this based epoxy resin (a1) individually or with two or more form of mixtures.
When the compound (a2) of phenolic hydroxy group comprises at least one being selected from pyrocatechol and alkyl pyrocatechol, pyrocatechol skeleton structure (a) can be introduced in the resin matrix of epoxy resin (A1).The example of alkyl pyrocatechol comprises 4-tert-butyl catechol, 4-methyl pyrocatechol, 2-methyl pyrocatechol etc.
The example of the compound of phenolic hydroxy group apart from the above (a2) comprises any compound that per molecule comprises at least one phenolic hydroxyl group.The example comprises two (4-hydroxy phenyls)-2, 2-propane [dihydroxyphenyl propane], two (4-hydroxy phenyl) methane [Bisphenol F], two (4-hydroxy-cyclohexyl) methane [A Hydrogenated Bisphenol A F], 2, two (4-hydroxy-cyclohexyl) propane [Hydrogenated Bisphenol A] of 2-, 4, 4 '-dihydroxy benaophenonel, two (4-hydroxy phenyls)-1, 1-ethane, two (4-hydroxy phenyls)-1, 1-Trimethylmethane, two (4-hydroxyl-2 or 3-tert-butyl-phenyls)-2, 2-propane, two (2 hydroxy naphthalene base) methane, four (4-hydroxy phenyls)-1, 1, 2, 2-ethane, 4, 4 '-dihydroxy-diphenyl sulfone, linear phenolic aldehyde, cresol-novolak etc.
Can be individually or with two or more form of mixtures, use the compound (a2) of this class phenolic hydroxy group.
Ratio for each component in epoxy resin (A1) preparation, the amount that epoxy resin (a1) mixes with the compound (a2) of phenolic hydroxy group is that the ratio of the phenolic hydroxyl group mole number in the compound (a2) of epoxy group(ing) mole number in epoxy resin (a1) and phenolic hydroxy group is 2.0 to 1.3, is preferably 2.0 to 1.35.When mol ratio is greater than 2.0, lower erosion resistance will be there is.When mol ratio is less than 1.3, poor finishability will be there is.Consider erosion resistance and the finishability of the obtained raising of filming, preferably with the ratio in above-mentioned scope, use the compound (a2) of epoxy resin (a1) and phenolic hydroxy group.
Conventionally, at 80 ℃ to 200 ℃, preferably at 90 ℃ to 180 ℃, can be by the compound (a2) of epoxy group(ing) (a1) and phenolic hydroxy group be reacted 1 hour to 6 hours under the existence of catalyzer, preferably within 1 hour to 5 hours, obtain the epoxy resin (A1) in a part for molecule with the pyrocatechol skeleton structure (a) being represented by general formula (1), described catalyzer for example, such as the tertiary amine of dimethyl benzylamine or tributylamine, or such as the quaternary ammonium salt of tetraethylammonium bromide or Tetrabutyl amonium bromide.
Epoxy resin (A1) can be the compound (a2) of epoxy resin (a1) and phenolic hydroxy group and the product of the partial reaction of polyvalent alcohol, polyether glycol, polyester polyol, daiamid, poly carboxylic acid, polyisocyanate compounds etc.; Or it can be the graft polymerization product of lactone such as 6-caprolactone, Acrylic Acid Monomer etc.
In the preparation of epoxy resin (A1), can be optionally with an organic solvent.The example of this class organic solvent comprises toluene, dimethylbenzene, hexanaphthene, normal hexane and similar varsol; Ritalin, vinyl acetic monomer, N-BUTYL ACETATE and similar esters solvent; Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone and similar ketones solvent; Dimethyl formamide, N,N-DIMETHYLACETAMIDE and similar amide solvent; Methyl alcohol, ethanol, n-propyl alcohol, Virahol and similarly alcohols agent; Phenylcarbinol, methylbenzyl alcohol and similar aromatic alkyl alcoholic solvent; Ethylene glycol monobutyl ether, diethylene glycol monoethyl ether and similar ether alcohol compounds; And their mixture.
amine compound (A2)
Can be for the preparation of cation epoxy resin of the present invention (A) by epoxy resin (A1) and the addition reaction of amine compound (A2).Amine compound (A2) is that amino is introduced to epoxy resin with cationization epoxy resin and comprised at least one and the cationization component of the reactive hydrogen of epoxy reaction.
The example that is used for the aminocompound (A2) of this object comprises: monoalkylamine or dialkylamine, for example monomethyl amine, dimethylamine, mono aminoethane, diethylamine, single isopropylamine, diisopropylamine, monobutyl amine and dibutylamine; Alkanolamine, for example monoethanolamine, diethanolamine, list (2-hydroxypropyl) amine, two (2-hydroxypropyl) amine, monomethyl monoethanolamine and single ethyl amido alcohol; Alkylene polyamine, for example the ketoimine product of quadrol, propylene diamine, butanediamine, hexanediamine, tetren, penten, diethyl amino propylamine, diethylenetriamine and Triethylenetetramine (TETA) and these polyamines; Alkylene imine, for example ethyleneimine and propyleneimine; And cyclammonium, for example piperazine, morpholine and pyrazine.Can also be by the amine obtaining by ketoimine primary amine as this amine compound.Can use this amine compound (A2) individually or with two or more form of mixtures.
In the addition reaction of epoxy resin (A1) and amine compound (A2), the ratio of each component is not particularly limited, and can suitably change according to the application target of electrodeposition coating composition etc.Total solids quality based on epoxy resin (A1) and amine compound (A2), the amount of epoxy resin (A1) is generally 70% mass ratio to 98% mass ratio, be preferably 75% mass ratio to 96% mass ratio, and the amount of amine compound (A2) is generally 2% mass ratio to 30% mass ratio, be preferably 4% mass ratio to 25% mass ratio.
Conventionally, at 80 ℃ to 170 ℃, be preferably at 90 ℃ to 150 ℃, in suitable solvent, addition reaction carried out 1 hour to 6 hours, be preferably 1 hour to 5 hours.The example that can be used for the solvent of described reaction comprises: varsol, for example toluene, dimethylbenzene, hexanaphthene and normal hexane; Esters solvent, for example ritalin, vinyl acetic monomer and N-BUTYL ACETATE; Ketones solvent, for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and Methyl amyl ketone; Amide solvent, for example dimethyl formamide and N,N-DIMETHYLACETAMIDE; Alcohols agent, for example methyl alcohol, ethanol, n-propyl alcohol and Virahol; Aromatic alkyl alcohols, for example phenylcarbinol and methylbenzyl alcohol; Ether alcohol compounds, for example ethylene glycol monobutyl ether and diethylene glycol monoethyl ether; And their mixture.
Solids content based on resin (A), cation epoxy resin (A) preferably comprises 3% mass ratio to 65% mass ratio, is preferably the pyrocatechol skeleton structure (a) of 5% mass ratio to 40% mass ratio.Consider the reduction that suppresses to deposit fusion bonding, water-dispersible and the throwing power of filming, based on solids content, preferably with the amount in above-mentioned scope, use the cation epoxy resin (A) that comprises pyrocatechol skeleton structure (a).
block polyisocyanate (B)
Due to the combination that cation electric deposition paint composition of the present invention comprises cation epoxy resin (A) and block polyisocyanate (B), therefore can prepare thermoset cation electric deposition paint composition.
Block polyisocyanate (B) is the addition reaction product that approaches stoichiometric polyisocyanate compounds and isocyanate-terminated dose.Polyisocyanate compounds for block polyisocyanate (B) can be known compound.The example of this class polyisocyanate compounds comprises: aromatic series, aliphatics or alicyclic polymeric isocyanate compound, toluylene group diisocyanate for example, eylylene diisocyanate, phenylene vulcabond, ditan-2, 2 '-vulcabond, ditan-2, 4 '-vulcabond, ditan-4, 4 '-vulcabond, thick MDI (polymethylene polyphenyl isocyanate), two (isocyanic ester methyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate etc., the cyclized polymer of these polyisocyanate compounds or biuret, and their combination.
Consider Corrosion Protection, such as toluylene group diisocyanate, eylylene diisocyanate, phenylene vulcabond, ditan-2,4 '-vulcabond, ditan-4, the aromatic poly-isocyanate compound of 4 '-vulcabond and thick MDI is particularly preferred.
By isocyanate-terminated dose of isocyanate group that is added into polyisocyanate compounds with blocked isocyanate base.Preferably, the block polyisocyanate compound obtaining by such interpolation is at room temperature stable; Yet when the stoving temperature that is heated to film (being generally 100 ℃ to 200 ℃), end-capping reagent decomposes to produce free isocyanate group.
The example that can be used for the end-capping reagent of block polyisocyanate (B) comprises methyl ethyl ketone oxime, cyclohexanone-oxime and similar oxime compound; Phenol, p-tert-butylphenol, cresols and similar oxybenzene compound; Propyl carbinol, 2-Ethylhexyl Alcohol and similar fatty alcohol; Phenylcarbinol, methylbenzyl alcohol and similar aromatic series alkyl alcohol; Ethylene glycol monobutyl ether, diethylene glycol monoethyl ether and similar ether alcohol compound; ε-caprolactam, butyrolactam and similar lactam compound etc.
Based on component (A) and total solids quality (B), the ratio of cation epoxy resin in cation electric deposition paint composition of the present invention (A) and block polyisocyanate (B) is: the amount of component (A) is generally 50% mass ratio to 90% mass ratio, is preferably 60% mass ratio to 85% mass ratio; And the amount of component (B) is generally 10% mass ratio to 50% mass ratio, be preferably 15% mass ratio to 40% mass ratio.
Aforementioned proportion is preferred, to realize excellent coating character, and for example the coating composition stability on hot-dip galvanized steel sheet and electrodeposition-coating suitability; And obtain to comprise and there is excellent finishability and Corrosion Protection, particularly under the desciccator diaphragm thickness of 10 μ m, there is the coated article that the cationic electrodeposition of excellent finishability and Corrosion Protection is filmed.
In the preparation of cation electric deposition paint composition, cation epoxy resin (A) and block polyisocyanate (B) are fully mixed, if desired, thus with such as tensio-active agent and the various additives such as surface conditioner, organic solvent mix and prepare resin.Thereby the resin of preparation is given water-soluble or water-dispersible and obtains emulsion by organic carboxyl acid etc.
Conventionally, use the neutralization of the resin that known organic carboxyl acid is prepared.Acetic acid, formic acid, lactic acid and composition thereof are particularly preferred.Subsequently, pigment disperse sizing agent is added to emulsion, described emulsion is used the dilutions such as ionized water there is bath solids content (bath solids conent) with generation and be generally 5% mass ratio to 40% mass ratio, being preferably 8% mass ratio to 25% mass ratio and pH is 1.5 to 9.0, is preferably 2.0 to 6.5 cation electric deposition paint composition.
The tinting pigment that the pulp bales of colo(u)rant dispersion is disperseed with fine particulate form with which, rust-stabilising pigment, pigment extender etc.For example, can prepare slurry by being incorporated to pigment dispersing resin, neutralizing agent, pigment etc. and making mixture carry out dispersion treatment in the dispersion mixer such as ball mill, sand mill or pebble mill.
Known resin can be used as pigment dispersing resin.The example comprises matrix resin, tertiary amine-type epoxy resin, quaternary epoxy resin, tertiary sulfonium salt type epoxy resin and the similar resin with hydroxyl and cation group.
Pigment is not had to special restriction, and the example of available pigment comprises: tinting pigment, for example titanium oxide, carbon black and red iron oxide; Pigment extender, for example clay, mica, barium oxide, calcium carbonate and silicon-dioxide; And rust-stabilising pigment, for example molybdophosphate aluminium, aluminium triphosphate and zinc oxide (zinc white).
For suppressing corrosion or antirust, can use bismuth compound.The example of this class bismuth compound comprises bismuth oxide, bismuth hydroxide, alkaline carbonic acid bismuth, Bismuth trinitrate, bismuth silicate, organic acid bismuth etc.
For improving the solidified nature of filming, can use the organo-tin compound such as dibenzoic acid dibutyl tin, di-n-octyltin oxide or dibutyltin oxide.Yet, can use and/or use rust-stabilising pigment and/or bismuth compound such as above-mentioned zinc oxide (zinc white) to replace these organo-tin compounds with fine particulate form with the amount increasing, to improve the solidified nature of filming.The matrix resin of every 100 mass parts and the total solids of solidifying agent, the amount of the pigment of use is preferably 1 mass parts to 100 mass parts, is in particular 10 mass parts to 50 mass parts.
The example that applies the base material of cation electric deposition paint composition of the present invention comprises the parts of body of a motor car, two wheeler, home appliances, miscellaneous equipment etc.As long as base material is by preparation of metals, it is not particularly limited.Example as the metal foil of base material comprises cold-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanizing steel plate, the two electroplating steel plates of electrolysis zinc-iron, organic double compound electroplating steel plate, aluminium base, magnesium substrates etc.If desired, can use these metals of washing such as alkaline degreasing method and make it carry out surface treatment, for example phosphate chemical conversion processing or chromic salt are processed.
By electrodeposition-coating, cation electric deposition paint composition can be coated on to the substrate surface of expectation.Therefore, the invention provides the electrodeposition-coating method as electrodeposition bath by above-mentioned electrodeposition coating composition, described method comprises step: base material is immersed in electrodeposition bath and by described base material and applies electric current as negative electrode.
More specifically, conventionally, by the temperature of electrodeposition bath being adjusted to 15 ℃ to 35 ℃ and base material is applied to electric current as negative electrode with the load voltage of 100V to 400V carry out cationic electrodeposition coating.Electrodeposition bath comprises electrodeposition coating composition, and its use deionized water etc. is diluted to the solids content of approximately 5% mass ratio to 40% mass ratio and has the pH that is adjusted to 5.5 to 9.0.Conventionally, after electrodeposition-coating, use the base material that fully washing applies such as ultrafiltrated (UF filtrate), reverse osmosis water (RO water), process water, deionized water to remove the cation electric deposition paint composition that is excessively bonded in base material.
The thickness of electrodeposition coating is not particularly limited, but thickness based on dry coating is generally 5 μ m to 40 μ m, is preferably 7 μ m to 30 μ m.By the dryer such as electric heating-air dryer or combustion gas heat-air dryer, be generally 110 ℃ to 200 ℃, be preferably under the surface temperature of coated article of 140 ℃ to 180 ℃, by electrodeposition coating heating is generally to 10 minutes to 180 minutes, be preferably 20 minutes to 50 minutes, thereby curing of filming is dry.By such, cure dryly, can obtain filming of solidifying.
By the above-mentioned cationic electrodeposition that cures dry acquisition, film, special at the desciccator diaphragm thickness place of 10 μ m, the center line average roughness having (Ra) is less than 0.30 μ m, is preferably less than 0.25 μ m (in cut-off place of 0.8mm); And there is excellent finishability.The center line average roughness of roughness curve (Ra) is defined by JIS B 601.
Embodiment
Below with reference to Preparation Example, embodiment and comparative example, explain the present invention; Yet the present invention is not limited.In an embodiment, " part " and " % " is based on quality meter.
the preparation of cation epoxy resin (A)
The Preparation Example (example) of 1: the No. 1 matrix resin of Preparation Example
The dimethyl benzylamine of the jER828EL of 760 parts (mark 1), the EPICLON HP-820 (mark 2) of 450 parts, the dihydroxyphenyl propane of 456 parts and 0.2 part is placed on to the 2-that is equipped with thermometer, reflux exchanger and agitator to be risen in removable flask.Mixture is reacted until epoxy equivalent (weight) becomes 833 at 120 ℃.Subsequently, the ethylene glycol monobutyl ether of 110 parts is added to mixture, then reaction at 100 ℃.
Adding the diethylenetriamine (purity is 84%, methyl isobutyl ketone solution) of diethanolamine and 95 parts of ketoimines of 158 parts and making after it reacts 4 hours at 120 ℃, add the ethylene glycol monobutyl ether of 289 parts.Obtain thus No. 1 substrate resin solution of the resin solid content with 80%.The amine value of No. 1 matrix resin is 64mg KOH/g, number-average molecular weight be 1,900 and pyrocatechol skeleton structure content be 18%.
The ratio of the phenolic hydroxyl group mole number in the compound (a2) of the epoxy group(ing) mole number in epoxy resin (a1) and phenolic hydroxy group is 1.5.
(mark 1) jER828EL: trade(brand)name, by Japan Epoxy Co., epoxy resin prepared by Ltd., epoxy equivalent (weight): 190, number-average molecular weight: 380
(mark 2) EPICLON HP-820: trade(brand)name, by make Epicholorohydrin be selected from pyrocatechol and alkyl pyrocatechol at least one react the epoxy resin obtaining, the product of DIC Corporation, epoxy equivalent (weight): 225, number-average molecular weight: 450
The Preparation Example (example) of 2: the No. 2 substrate resin solutions of Preparation Example
The dimethyl benzylamine of the jER828EL of 1,140 part (mark 1), the pyrocatechol of 220 parts and 0.2 part is placed on to the 2-that is equipped with thermometer, reflux exchanger and agitator to be risen in removable flask.Mixture is reacted until epoxy equivalent (weight) becomes 680 at 120 ℃.Subsequently, add the ethylene glycol monobutyl ether of 110 parts and mixture is reacted at 100 ℃.
Subsequently, add the diethylenetriamine (purity is 84%, methyl isobutyl ketone solution) of diethanolamine and 95 parts of ketoimines of 158 parts, and mixture is reacted 4 hours at 120 ℃, after this add the ethylene glycol monobutyl ether of 211 parts.Obtain thus No. 2 substrate resin solution of the resin solid content with 80% mass ratio.The amine value of No. 2 matrix resin is 76mgKOH/g, number-average molecular weight be 1,500 and pyrocatechol skeleton structure be 14%.
The ratio of the phenolic hydroxyl group mole number in the compound (a2) of the epoxy group(ing) mole number in epoxy resin (a1) and phenolic hydroxy group is 1.5.
The Preparation Example (example) of 3: the No. 3 substrate resin solutions of Preparation Example
The dimethyl benzylamine of the jER828EL of 1,140 part (mark 1), the tert-butyl catechol of 332 parts and 0.2 part is placed on to the 2-that is equipped with thermometer, reflux exchanger and agitator to be risen in removable flask.Mixture is reacted until epoxy equivalent (weight) becomes 736 at 120 ℃.Subsequently, add the ethylene glycol monobutyl ether of 110 parts, and mixture is reacted at 100 ℃.
Subsequently, add the diethylenetriamine (purity is 84%, methyl isobutyl ketone solution) of diethanolamine and 95 parts of ketoimines of 158 parts, and mixture is reacted 4 hours at 120 ℃, after this add the ethylene glycol monobutyl ether of 241 parts.Obtain thus No. 3 substrate resin solution of the resin solid content with 80%.The amine value of No. 3 matrix resin is 71mg KOH/g, number-average molecular weight be 1,700 and pyrocatechol skeleton structure be 20%.
The ratio of the phenolic hydroxyl group mole number in the compound (a2) of the epoxy group(ing) mole number in epoxy resin (a1) and phenolic hydroxy group is 1.5.
The Preparation Example (example) of 4: the No. 4 substrate resin solutions of Preparation Example
The dimethyl benzylamine of the jER828EL of 1,634 part (mark 1), the tert-butyl catechol of 548 parts and 0.2 part is placed on to the 2-that is equipped with thermometer, reflux exchanger and agitator to be risen in removable flask.Mixture is reacted until epoxy equivalent (weight) becomes 798 at 120 ℃.Subsequently, add the ethylene glycol monobutyl ether of 110 parts, and mixture is reacted at 100 ℃.
Subsequently, add the diethylenetriamine (purity is 84%, methyl isobutyl ketone solution) of diethanolamine and 95 parts of ketoimines of 158 parts, and mixture is reacted 4 hours at 120 ℃, after this add the ethylene glycol monobutyl ether of 419 parts.Obtain thus No. 4 substrate resin solution of the resin solid content with 80%.
The amine value of No. 4 matrix resin is 50mg KOH/g, number-average molecular weight be 2,300 and pyrocatechol skeleton structure content be 23%.The ratio of the phenolic hydroxyl group mole number in the compound (a2) of the epoxy group(ing) mole number in epoxy resin (a1) and phenolic hydroxy group is 1.3.
The Preparation Example (example) of 5: the No. 5 substrate resin solutions of Preparation Example
The dimethyl benzylamine of the jER828EL of 760 parts (mark 1), the tert-butyl catechol of 166 parts and 0.2 part is placed on to the 2-that is equipped with thermometer, reflux exchanger and agitator to be risen in removable flask.Mixture is reacted until epoxy equivalent (weight) becomes 418 at 120 ℃.Subsequently, add the ethylene glycol monobutyl ether of 110 parts, and mixture is reacted at 100 ℃.
Subsequently, add the diethylenetriamine (purity is 84%, methyl isobutyl ketone solution) of diethanolamine and 95 parts of ketoimines of 200 parts, and mixture is reacted 4 hours at 120 ℃, after this add the ethylene glycol monobutyl ether of 104 parts.Obtain thus No. 5 substrate resin solution of the resin solid content with 80%.The amine value of No. 5 matrix resin is 106mg KOH/g, number-average molecular weight be 1,200 and pyrocatechol skeleton structure content be 15%.
The ratio of the phenolic hydroxyl group mole number in the compound (a2) of the epoxy group(ing) mole number in epoxy resin (a1) and phenolic hydroxy group is 2.0.
The Preparation Example of 6: the No. 6 substrate resin solutions of Preparation Example
The dimethyl benzylamine of the jER828EL of 1,140 part (mark 1), the dihydroxyphenyl propane of 456 parts and 0.2 part is placed on to the 2-that is equipped with thermometer, reflux exchanger and agitator to be risen in removable flask.Mixture is reacted until epoxy equivalent (weight) becomes 1965 at 120 ℃.Subsequently, add the ethylene glycol monobutyl ether of 110 parts, and mixture is reacted at 100 ℃.
Subsequently, add the diethylenetriamine (purity is 84%, methyl isobutyl ketone solution) of diethanolamine and 95 parts of ketoimines of 158 parts, and mixture is reacted 4 hours at 120 ℃, after this add the ethylene glycol monobutyl ether of 211 parts.Obtain thus No. 6 substrate resin solution of the resin solid content with 80%.The amine value of No. 6 matrix resin is 66mg KOH/g, number-average molecular weight be 1,800 and pyrocatechol skeleton structure content be 0%.
The ratio of the phenolic hydroxyl group mole number in the compound (a2) of the epoxy group(ing) mole number in epoxy resin (a1) and phenolic hydroxy group is 1.5.
The Preparation Example of 7: the No. 7 substrate resin solutions of Preparation Example
The dimethyl benzylamine of the jER828EL of 684 parts (mark 1), the tert-butyl catechol of 133 parts and 0.2 part is placed on to the 2-that is equipped with thermometer, reflux exchanger and agitator to be risen in removable flask.Mixture is reacted until epoxy equivalent (weight) becomes 418 at 120 ℃.Subsequently, add the ethylene glycol monobutyl ether of 110 parts, and mixture is reacted at 100 ℃.
Subsequently, add the diethylenetriamine (purity is 84%, methyl isobutyl ketone solution) of diethanolamine and 95 parts of ketoimines of 158 parts, and mixture is reacted 4 hours at 120 ℃, after this add the ethylene glycol monobutyl ether of 78 parts.Obtain thus No. 7 substrate resin solution of the resin solid content with 80%.The amine value of No. 7 matrix resin is 117mg KOH/g, number-average molecular weight be 1,200 and pyrocatechol skeleton structure content be 13%..
The ratio of the phenolic hydroxyl group mole number in the compound (a2) of the epoxy group(ing) mole number in epoxy resin (a1) and phenolic hydroxy group is 2.3.
The Preparation Example of 8: the No. 8 substrate resin solutions of Preparation Example
By the jER828EL of 2,280 parts (mark 1), the dimethyl benzylamine of the dihydroxyphenyl propane of 580 parts and 0.2 part is placed on the 2-that is equipped with thermometer, reflux exchanger and agitator and rises in removable flask.Mixture is reacted until epoxy equivalent (weight) becomes 1965 at 120 ℃.Subsequently, add the ethylene glycol monobutyl ether of 110 parts, and mixture is reacted at 100 ℃.Subsequently, add the diethylenetriamine (purity is 84%, methyl isobutyl ketone solution) of diethanolamine and 95 parts of ketoimines of 158 parts, and mixture is reacted 4 hours at 120 ℃, after this add the ethylene glycol monobutyl ether of 588 parts.Obtain thus No. 8 substrate resin solution of the resin solid content with 80%.The amine value of No. 8 matrix resin is 39mg KOH/g, number-average molecular weight be 2,500 and pyrocatechol skeleton structure content be 19%.The ratio of the phenolic hydroxyl group mole number in the compound (a2) of the epoxy group(ing) mole number in epoxy resin (a1) and phenolic hydroxy group is 1.2.
Lower list 1 illustrates the formula of Preparation Example 1 to 8.
the preparation of block polyisocyanate (B)
Preparation Example 9: the Preparation Example of solidifying agent
The methyl iso-butyl ketone (MIBK) of the Cosmonate M-200 of 270 parts (mark 3) and 127 parts is placed in reaction vessel and is heated to 70 ℃.Drip wherein the ethylene glycol monobutyl ether of 236 parts, the time is 1 hour, and mixture is heated to 100 ℃.When keeping this temperature, in time mixture is sampled.By infrared absorption spectrum, observed the absorption that there is no unreacted isocyanate groups.Obtain thus the solidifying agent of the resin solid content with 80%.
(mark 3) Cosmonate M-200: trade(brand)name, by Mitsui Chemicals, the thick MDI that Inc. produces.
Preparation Example 10: the Preparation Example of pigment dispersing resin
The jER828EL of 1,010 part (referring to mark 1) is mixed with the dihydroxyphenyl propane of 390 parts, the PLACCEL 212 of 240 parts (mark 4) and the dimethyl benzylamine of 0.2 part, and mixture is reacted until epoxy equivalent (weight) becomes approximately 1,090 at 130 ℃.
Subsequently, add the dimethylethanolamine of 134 parts and 90% lactic acid aqueous solution of 150 parts, and mixture is reacted 4 hours at 120 ℃.After this, add methyl iso-butyl ketone (MIBK) to regulate solids content.Obtain thus the ammonium salt resin type pigment dispersing resin of the solids content with 60%.The ammonium salt concentration of pigment dispersing resin is 0.78mmol/g.
(mark 4) PLACCEL 212: trade(brand)name, by Daicel Chemical Industries, the polycaprolactone glycol that Ltd. produces, weight-average molecular weight: approximately 1,250
Preparation Example 11: the Preparation Example of the slurry of colo(u)rant dispersion
The pigment dispersing resin that the solids content that adds 8.3 parts (5 parts of solids) to obtain in Preparation Example 10 is 60%, the titanium oxide of 14.5 parts, the refined clay of 7.0 parts, the carbon black of 0.3 part, the di-n-octyltin oxide of 1 part, the bismuth hydroxide of 1 part and the deionized water of 20.3 parts, and in ball mill, disperse 20 hours.Obtain thus the slurry of the colo(u)rant dispersion of the solids content with 55%.
the preparation of emulsion
The Preparation Example of 12: the No. 1 emulsions of Preparation Example
Solidifying agent that No. 1 matrix resin that 87.5 parts (solids contents: 70 parts) are obtained in Preparation Example 1 and 37.5 parts (solids content: 30 parts) obtain in Preparation Example 9 mixes, and adds 10% the formic acid of 12.1 parts.After by mixture uniform stirring, in approximately 15 minutes, drip the deionized water of 156.9 parts, while vigorous stirring, thus obtain No. 1 emulsion that solids content is 34%.
Preparation Example 13 is to the Preparation Example of 19: the 2 to No. 8 emulsions
Except using the formula shown in table 2, in the mode identical with Preparation Example 12, obtain emulsion the 2nd to No. 8.
Table 2
Bracketed numeral solids content in formula.
the preparation of cation electric deposition paint composition
Embodiment 1
Add No. 1 emulsion that 294 parts (solids contents: 100 parts) obtain in Preparation Example 12,55% pigment disperse sizing agent that 52.4 parts (solids content: 28.8 parts) obtains in Preparation Example 9 and the deionized water of 297.6 parts.Obtain thus solids content and be 20% No. 1 cation electric deposition paint composition.
Embodiment 2 to 5 and comparative example 1 to 3
Except using the formula shown in table 3, in the mode identical with Preparation Example 1, prepare cation electric deposition paint composition the 2nd to No. 8.
Table 3
Bracketed numeral solids content in formula.
the preparation that comprises the plate that cationic electrodeposition films
Using the cold-rolled steel sheet (70mm * 150mm * 0.8mm) of processing through chemical conversion immerse adjusted be during the 1st to No. 8 cation electric deposition paint compositions of 28 ℃ are bathed as " base material " to carry out electrodeposition-coating under 250V, adjusting simultaneously applies the time of electric current.Thereby the film of generation being cured at 170 ℃ and within 20 minutes, obtain desciccator diaphragm thickness is the test panel of 10 μ m and 20 μ m.Evaluate under the following conditions each test panel.Table 4 illustrates result.
Table 4
(mark 5) throwing power: as shown in Figure 2, will there are " four layers of box throwing power test fixture " (referring to Fig. 1) and four steel plate installing wires of placing with 2cm interval of 8mm diametric hole.In four block plates shown in Fig. 2, the left surface of Far Left steel plate is called to " surface A " and its right surface is called to " surperficial B ".Similarly, left surface from left side number the second block plate and right surface are called to " surface C " and " surperficial D ", left surface from left side number the 3rd block plate and right surface are called to " surperficial E " and " surperficial F ", and the left surface of rightmost steel plate and right surface are called to " surperficial G " and " surperficial H ".Surface A is equivalent to " outside plate " and surperficial G is equivalent to " inner panel ".
Use the device shown in Fig. 2, carry out under the following conditions electrodeposition-coating: coating bath temperature is 28 ℃, the distance between surface A and electrode is 10cm, and electric current application time is 3 minutes and is the required voltage of outside plate desciccator diaphragm thickness that obtains 15 μ m.Based on outside plate desciccator diaphragm thickness, inner panel desciccator diaphragm thickness and throwing power (%) (=inner panel desciccator diaphragm thickness/outside plate desciccator diaphragm thickness * 100), evaluate throwing power.
(mark 6) finishability: according to JIS B 0601 (Definition and Indication of Surface Roughness (definition of surfaceness and sign), 1982), use Surfcom301 (trade(brand)name, the surface roughness measuring instrument of being manufactured by Mitutoyo Corporation) to detect the center line average roughness (Ra) of each electrodeposition coating (desciccator diaphragm thickness: 10 μ m and 20 μ m) obtaining in embodiment and comparative example.According to " center line average roughness (Ra) " of following each electrodeposition coating of standard evaluation:
S:Ra is less than 0.25.
A:Ra is not less than 0.25 and be less than 0.30.
B:Ra is not less than 0.30 and be less than 0.40.
C:Ra is not less than 0.40.
(mark 7) Corrosion Protection: be that each test panel that the cationic electrodeposition of 10 μ m or 20 is filmed carries out crosscut so that otch reaches base material to being included in the desciccator diaphragm thickness obtaining in embodiment and comparative example with cutter.Then, according to JIS Z-2371, at 35 ℃, make each test panel carry out the salt-fog test of 480 hours (desciccator diaphragm thickness is 10 μ m) or 840 hours (desciccator diaphragm thickness is 20 μ m).According to following standard, the width of the corrosion based on otch or gas blister is evaluated Corrosion Protection:
S: the maximum width of the corrosion of otch or gas blister is not more than 2.0mm (in one side).
A: the maximum width of the corrosion of otch or gas blister is greater than 2.0mm and is not more than 3.0mm (in one side).
B: the maximum width of the corrosion of otch or gas blister is greater than 3.0mm and is not more than 3.5mm (in one side).
C: the maximum width of the corrosion of otch or gas blister is greater than 3.5mm (in one side).(mark 8) comprehensive evaluation
At the cathode electrodeposition the present invention relates to, apply field, the excellent throwing power of filming obtaining and excellent finishability and Corrosion Protection are expected.Therefore, according to following standard comprehensive evaluation cation electric deposition paint composition:
S: throwing power is not less than 60%, and the Corrosion Protection of the Corrosion Protection of the finishability of the finishability of 10 μ m desciccator diaphragm thickness, 20 μ m desciccator diaphragm thickness, 10 μ m desciccator diaphragm thickness and 20 μ m desciccator diaphragm thickness is all evaluated as " S " or " A ", and at least one in these performances is evaluated as " S ".
A: throwing power is not less than 60%, and the finishability of 10 μ m desciccator diaphragm thickness, the finishability of 20 μ m desciccator diaphragm thickness are, the Corrosion Protection of the Corrosion Protection of 10 μ m desciccator diaphragm thickness and 20 μ m desciccator diaphragm thickness is all evaluated as " A ".
B: throwing power is not less than 60%, and the Corrosion Protection of the Corrosion Protection of the finishability of the finishability of 10 μ m desciccator diaphragm thickness, 20 μ m desciccator diaphragm thickness, 10 μ m desciccator diaphragm thickness and 20 μ m desciccator diaphragm thickness is all evaluated as " S ", " A " or " B ", and at least one in these performances is evaluated as " B ".
C: throwing power is not less than 60%, or the finishability of 10 μ m desciccator diaphragm thickness, the finishability of 20 μ m desciccator diaphragm thickness are, at least one in the Corrosion Protection of the Corrosion Protection of 10 μ m desciccator diaphragm thickness and 20 μ m desciccator diaphragm thickness is evaluated as " C ".
Industrial usability
Can provide there is excellent throwing power, the coated article of excellent film finishability and excellent film Corrosion Protection.
The description of reference number
1. hole (diameter is 8mm)
2. the outside plate (surface A) of four layers of box throwing power test fixture
3. the inner panel of four layers of box throwing power test fixture (surperficial G)
4. electrocoating paint is bathed
Claims (6)
1. cation electric deposition paint composition, it comprises cation epoxy resin (A) and block polyisocyanate (B),
By making epoxy resin (A1) react to obtain described cation epoxy resin (A) with the compound (A2) containing amino, and
Described epoxy resin (A1) has the pyrocatechol skeleton structure (a) being represented by following general formula (1) in a part for molecule
Wherein R represents hydrogen atom or has the alkyl of 1 to 6 carbon atom, and react and obtain by the compound (a2) that makes per molecule comprise at least one epoxy group(ing) and to there is the phenolic hydroxy group that the epoxy resin (a1) of 180 to 500 epoxy equivalent (weight)s comprises at least one phenolic hydroxyl group with per molecule, the amount of the compound (a2) of described epoxy resin (a1) and described phenolic hydroxy group is that the ratio of the mole number of phenolic hydroxyl group in the middle mole number of epoxy group(ing) of described epoxy resin (a1) and the compound of described phenolic hydroxy group (a2) is 1.3 to 2.0, the solids content based on described resin (A) wherein, the described pyrocatechol skeleton structure (a) that described cation epoxy resin (A) comprises 3% mass ratio to 65% mass ratio.
2. cation electric deposition paint composition as claimed in claim 1, wherein said epoxy resin (a1) comprise by make Epicholorohydrin be selected from pyrocatechol and alkyl pyrocatechol at least one react the epoxy resin obtaining.
3. cation electric deposition paint composition as claimed in claim 1, the compound of wherein said phenolic hydroxy group (a2) comprises at least one being selected from pyrocatechol and alkyl pyrocatechol.
4. cation electric deposition paint composition as claimed in claim 1, the solids content based on described resin (A) wherein, the described pyrocatechol skeleton structure (a) that described cation epoxy resin (A) comprises 5% mass ratio to 40% mass ratio.
5. cation electric deposition paint composition as claimed in claim 1, the R in its formula of (1) represents to have the alkyl of 4 to 6 carbon atoms.
6. electrodeposition-coating method, it comprises step: base material is immersed in electrodeposition bath, wherein by cation electric deposition paint composition claimed in claim 1 as described electrodeposition bath, and by described base material as negative electrode and apply electric current.
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| EP2147955A1 (en) * | 2008-07-21 | 2010-01-27 | Cytec Surface Specialties Austria GmbH | Aqueous coating binders for corrosion protection, wood and concrete |
| CA2925359A1 (en) * | 2013-11-18 | 2015-05-21 | Basf Coatings Gmbh | Aqueous dip-coating composition for electroconductive substrates, comprising both dissolved and undissolved bismuth |
| US10308822B2 (en) | 2014-11-19 | 2019-06-04 | Kansai Paint Co., Ltd. | Thermosetting coating composition |
| US10280251B2 (en) | 2015-03-17 | 2019-05-07 | Toray Industries, Inc. | Epoxy resin composition, prepreg, and carbon fiber-reinforced composite material |
| CN108003750A (en) * | 2017-12-21 | 2018-05-08 | 苏州希尔盖森新材料有限公司 | A kind of corrosion resistant cathode electrophoretic coating composition |
| US11186734B2 (en) * | 2019-05-31 | 2021-11-30 | Axalta Coating Systems Ip Co., Llc | Epoxy resin emulsions for electrocoating |
| CN115873216B (en) * | 2022-12-26 | 2023-12-05 | 浙江工业大学 | Novel grinding resin for antibacterial electrophoretic coating color paste and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3627720A (en) * | 1967-02-13 | 1971-12-14 | Ciba Ltd | Epoxide-containing compositions |
| CN1162330A (en) * | 1994-10-25 | 1997-10-15 | Ppg工业公司 | Electrodepositable coating composition having improved cure response |
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| JP2002069154A (en) * | 2000-08-30 | 2002-03-08 | Dainippon Ink & Chem Inc | Epoxy resin composition |
| US6500912B1 (en) * | 2000-09-12 | 2002-12-31 | Resolution Performance Products Llc | Epoxy resin system |
| JP2004043661A (en) * | 2002-07-12 | 2004-02-12 | Dainippon Ink & Chem Inc | Coating material composition |
| JP2009179859A (en) * | 2008-01-31 | 2009-08-13 | Nippon Paint Co Ltd | Method for forming multilayer coating film |
| JP2009256491A (en) * | 2008-04-17 | 2009-11-05 | Kansai Paint Co Ltd | Cationic electrodeposition coating composition |
| JP2010037481A (en) * | 2008-08-07 | 2010-02-18 | Nippon Paint Co Ltd | Cationic electrodeposition paint composition and cationic electrodeposition coating method |
| JP5441802B2 (en) | 2009-05-26 | 2014-03-12 | 関西ペイント株式会社 | Cationic electrodeposition coating composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3627720A (en) * | 1967-02-13 | 1971-12-14 | Ciba Ltd | Epoxide-containing compositions |
| CN1162330A (en) * | 1994-10-25 | 1997-10-15 | Ppg工业公司 | Electrodepositable coating composition having improved cure response |
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| JP2012197431A (en) | 2012-10-18 |
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